KR101774126B1 - Hydrocarbon processes using uzm-43 an euo-nes-non zeolite - Google Patents

Abstract

In the present invention, a new class of crystalline aluminosilicate zeolite designated UZM-43 is synthesized. This zeolite is similar to the conventionally known ERS-10, SSZ-47 and RUB-35 zeolites, but features a unique x-ray diffraction pattern and composition and possesses various catalytic properties for carrying out various hydrocarbon conversion processes. Catalysts made from such zeolites are useful in hydrocarbon conversion processes.

Description

UZM-43 EUO-NES-NON ZEOLITE (HYDROCARBON PROCESSES USING UZM-43 AN EUO-NES-NON ZEOLITE)

Priority Claim of Initial National Application

This application claims priority to application No. 13 / 718,003, filed December 18, 2012, which claims priority.

Field of invention

The present application relates to zeolite UZM-43, its preparation process and its use as a catalyst in a hydrocarbon conversion process. This zeolite is represented by the following empirical formula:

에 의해 결정된 값을 갖는다. 그 제올라이트 UZM-43은 골격 EUO-NES-NON의 연정(intergrowth)을 갖는다. 그것은 미개질형 UZM-43 제올라이트로서 또는 개질형 UZM-43 제올라트로서 촉매 내에 존재할 수 있다, UZM-43 함유 촉매는 예를 들어 구상 유적형 촉매 또는 압출형 촉매를 포함하는 여러 형태 중 하나를 취할 수 있다.Wherein m represents sodium or represents a combination of sodium and potassium exchangeable cations, "m" is the molar ratio of M to (Al + E) and varies from 0.05 to 5, and R1 is a single charged Quot; rl "is the molar ratio of R to (Al + E) and has a value of 0.25 to 8.0, R2 is an amine," r2 " X is the molar fraction of E and has a value of from 0 to 1.0, and "y" is the mole fraction of (Al +) and E is the element selected from the group consisting of gallium, iron, boron and mixtures thereof, E) is changed from more than 5 to 40, "z" is the molar ratio of O to (Al + E), and the equation:

Lt; / RTI > The zeolite UZM-43 has an intergrowth of the skeleton EUO-NES-NON. It may be present in the catalyst as unmodified UZM-43 zeolite or as a modified UZM-43 zeolite. The UZM-43 containing catalyst may be in one of several forms including, for example, I can take it.

Zeolite is a crystalline aluminosilicate composition that is microporous and is formed from corners that share the AlO ₂ and SiO ₂ tetrahedra. Many zeolites, both naturally occurring and synthetically produced, are used in a variety of industrial processes. Synthetic zeolites are prepared via hydrothermal synthesis using suitable sources of Si, Al and structure directing agents such as alkali metals, alkaline earth metals, amines or organic ammonium cations. The structure-directing agents remain in the pores of the zeolite, and are the major contributor to the specific structure ultimately formed. These species maintain the balance of the skeletal charge associated with aluminum and can also act as space fillers. The zeolite is characterized by having pore openings of uniform size, having a significant ion exchange capacity, and capable of reversibly desorbing the adsorbed phase, wherein the phase comprises any atom constituting a permanent zeolite crystal structure Are dispersed all around the inner pores of the crystal without significant substitution. The zeolite can be used as a catalyst for the hydrocarbon conversion reaction which can take place on the outer surface as well as on the inner surface in the pore.

The three structural types EUO, NON and NES are closely related and can be constructed from the same two layer building units, LBU A and LBU B, shown below, extending in the a 'and b' axes directions. LBU A consists of a TO ₄ tetrahedron connected in two dimensions to produce a silicate sheet with a 12 ring opening. LBU B consists of a linear chain of TO ₄ tetrahedra. In order to create a three-dimensional framework structure for EUO, NON and NES, the two layer types are stacked in a characteristic sequence in the c 'axis direction.

The diagram shows the layer-like constituent units of the EUO-NES-NON family as shown by the normal line for (0 0 1). (a) Layer A is composed of a [TO ₄ ] tetrahedron interconnected to form a 12-membered ring, and (b) layer B is composed of a rod of [TO ₄ ] tetrahedron that runs parallel to the a 'axis.

The Diagram shows a representation of the skeletal structure and stacking order for (a) NON, (b) EUO and (c) NES, as shown by the normal lines for (1 0 0).

a) In the case of NON, only the LBU A layer is deposited. The stacking order is AA'AA ', where all other A layers are shifted by 1 / 2a' and designated as A '. Even though the individual layers contain 12-member rings, the alternating movement of 1 / 2a ' blocks access and the resulting NON skeleton becomes a dense phase. This is actually a clatrasil, not a zeolite, because it contains a cage (designated nns by J.V. Smith 1) accessible by a pore not larger than the six-membered ring.

b) The EUO backbone pattern can be formed by inserting a B layer between the AA 'double layers to create a stacking sequence AA'BAA'B. The resulting skeleton contains a one-dimensional 10-member circular channel with side pockets in a truncated nns cage.

c) The NES skeletal pattern can be formed by alternating layer A and layer B to create a stacking sequence AB'A'BAB'A'B where A 'and B' are shifted by 1 / 2a '. The resulting skeleton contains a two-dimensional ten-member ring channel that is normal to the b 'axis.

Although several related molecular sieves have been disclosed, there is a significant difference between these molecular sieves and the molecular sieves of the present invention. US Pat. No. 123,914 discloses EUO-NES type solids and EU-1 of molecular sieves used to remove amorphous B and aluminum from the channels using mild conditions by sodium hydroxide. The present invention includes a silica / alumina material that does not contain boron.

US 7,459,073 discloses a molecular sieve SSZ-47B which is prepared using a rigid template (N-cyclopentyl-1,4-diabicyclo [2.2.2] octane cation) There is a tendency to produce zeolites that are too expensive to manufacture and have larger EUO characteristics than other materials.

US 5,910,299 discloses ERS-10 zeolites prepared using templates such as 6-azonia spiro- [5,5] -undecane hydroxide. It is claimed to have a Si / Al ₂ ratio of from 50 to pure silica. The present invention is made with Si / Al ₂ ratios lower than ERS-10.

In the present invention, a novel material comprising an EUO-NES-NON skeletal system applied in a hydrocarbon process was prepared.

Summary of the Invention

As described, the present invention relates to a novel aluminosilicate zeolite designated UZM-43, which comprises the EUO-NES-NON skeletal ring. Thus, one embodiment of the present invention is a microporous crystalline zeolite having at least three-dimensional frameworks of AlO ₂ and SiO ₂ tetrahedral units, and an as-synthesized as-synthesized and anhydrous-

에 의해 결정된 값을 가지며,Wherein m represents sodium or represents a combination of sodium and potassium exchangeable cations, "m" is the molar ratio of M to (Al + E) and varies from 0.05 to 5, and R1 is a single charged Quot; rl "is the molar ratio of R to (Al + E) and has a value of 0.25 to 8.0, R2 is an amine," r2 " X is the molar fraction of E and has a value of from 0 to 1.0, and "y" is the mole fraction of (Al +) and E is the element selected from the group consisting of gallium, iron, boron and mixtures thereof, E) is changed from more than 5 to 40, "z" is the molar ratio of O to (Al + E), and the equation:

Lt; RTI ID = 0.0 > a < / RTI &

Characterized in that the zeolite has an x-ray diffraction pattern with at least the d-spacing and strength shown in Table A below.

[Table A]

After calcination, the x-ray diffraction pattern shown in Table B below was observed.

[Table B]

Another embodiment of the present invention is a process for making such a material using a propyltrimethylammonium cation (SACHEM) or a propyltrimethylammonium cation and an amine. The prior art SSZ-47 material produces a material with much more EUO traits than the material produced by the present invention and is much more expensive than N, N-dimethyl-3-azonia bicyclo [4.2.1] N, N-dimethyl-3-azonia bicyclo [3.2.1] octane cations. ERS-10 produces zeolite materials made using another expensive template 6-azonia spiro [5,5] -undecane hydroxide and having a higher Si / Al ₂ ratio than UZM-43.

Another embodiment of the present invention is a hydrocarbon conversion process using the zeolite described above. The process comprises contacting the zeolite with a hydrocarbon under conversion conditions to produce a converted hydrocarbon product. The hydrocarbon process involves paraffin decomposition, aromatic conversion such as xylene isomerization, toluene disproportionation, ring opening and cracking to remove benzene n-co-boilers, and alkylation of aromatics with paraffins do.

Figure 1 shows the layer-like constituent units of the EUO-NES-NON family as shown by the normal line for (0 0 1).
Figure 2 shows a depiction of the skeletal structure and stacking order for (a) NON, (b) EUO and (c) NES as shown by the normal lines for (1 0 0).

DETAILED DESCRIPTION OF THE INVENTION

Applicants have found that the zeolite topology is described in the Atlas of Zeolite Framework Types maintained by the International Zeolite Association Rescue Committee with the address http://topaz.ethz.ch/IZA-SC/StdAtlas.htm To produce aluminosilicate zeolites which are similar to the RUB-35, SSZ-47 and ERS-10 types of zeolites and belong to the EUO-NES-NON framework. This new zeolite was designated as UZM-43. As shown in detail, UZM-43 differs from known zeolites in many of its features.

As detailed in the examples, the UZM-43 material is thermally stable up to at least 600 < 0 > C temperature and in yet another embodiment at least 800 < 0 > C. In addition, as shown in the examples, the UZM-43 material can have a micropore volume of greater than 60% as a percentage of the total pore volume.

The UZM material is prepared from the reaction mixture having the indicated composition in terms of the molar ratio of the oxides of the empirical formula shown below.

Wherein "a" has a value of 0.05 to 5.0, "b" has a value of 1.5 to 4.0, "c" has a value of 0 to 1.0, and "d" has a value of 4 to 40 Quot; e "has a value of 25 to 4,000. The source of M is selected from the group consisting of halide salts, nitrate salts, acetate salts, hydroxides, sulfate salts and mixtures thereof.

The source of E is selected from the group consisting of alkali borates, boric acid, precipitated gallium oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride, and mixtures thereof. The source of aluminum is selected from the group consisting of aluminum isopropoxide, aluminum sec-butoxide, precipitated alumina, Al (OH) ₃ , aluminum metal and aluminum salts. The silicon source is selected from the group consisting of tetraethylorthosilicate, fumed silica, colloidal silica and precipitated silica. The reaction mixture is reacted at a temperature of 150 ° C to 185 ° C for a period of 1 day to 3 weeks. Preferably, the reaction mixture is reacted at a temperature of 165 ° C to 175 ° C for a period of one to three weeks. R1 is a single charged propyl trimethylammonium cation, "rl" is the molar ratio of R to (Al + E) and has a value of from 0.25 to 8.0, R2 is an amine, and r2 is morpholine. The process may further comprise adding the UZM-43 seed to the reaction mixture.

Example

Example 1

The aluminosilicate reaction gel was prepared by first adding, under vigorous stirring, 48.92 g of liquid sodium aluminate (LSA) (46.55% solution), 225.23 g of propyltrimethylammonium hydroxide (20% SACHEM), 36.11 g of morpholine (Aldrich) and 865.38 g . After complete mixing, 224.36 g of Ultrasil VN SP 89% was added. After this addition was complete, the resulting reaction mixture was homogenized for 1 hour and transferred to a 2 L Parr stainless steel stirred autoclave. The mixture crystallized at 175 DEG C with stirring at 250 RPM for 160 hours. The solid product was recovered by centrifugation, washed with deionized water and dried at 95 < 0 > C. This product was identified as being UZM-43 by XRD. Representative diffraction lines observed for the product are shown in Table 1 below. The product composition was determined by elemental analysis to have the following molar ratios: Si / Al = 13.76 and Na / Al = 0.23. A portion of the material was calcined by ramping in air at 600 ° C for 2 hours and then residence for 6 hours. The BET surface area was 176 m ² / g and the micropore volume was 0.07 cc / g. According to a scanning electron microscope (SEM), it was confirmed that the crystal had a round (grape-like) shape of less than 100 nm. The chemical analysis was as follows: 3.06% Al, 42.9% Si, 0.99% Na, N / Al = 0.78, Na / Al = 0.38, Si / Al ₂ = 27. The diffraction lines observed for UZM- 1 < / RTI >

[Table 1]

Representative diffraction lines observed for the calcined UZM-43 are shown in Table 2 below.

[Table 2]

Example 2

The aluminosilicate reaction gel was prepared by first adding, under vigorous stirring, 48.92 g of liquid sodium aluminate (LSA) (46.55% solution), 225.23 g of propyltrimethylammonium hydroxide (20% SACHEM), 36.11 g of morpholine (Aldrich) and 865.38 g . After complete mixing, 224.36 g of Ultrasil VN SP 89% was added. After this addition was complete, the resulting reaction mixture was homogenized for 1 hour and transferred to a 2 L Parr stainless steel stirred autoclave. The mixture crystallized at 175 DEG C with stirring at 350 RPM for 160 hours. The solid product was recovered by centrifugation, washed with deionized water and dried at 95 < 0 > C. This product was identified as being UZM-43 by XRD. Representative diffraction lines observed for the product are shown in Table 3 below. The product composition was determined by elemental analysis to have the following molar ratios: Si / Al = 13.5, Na / Al = 0.38 and N / Al = 0.78. A portion of the material was calcined in air for 2 hours at 600 DEG C and then for 6 hours. The BET surface area was 192 m ² / g and the micropore volume was 0.07 cc / g. According to a scanning electron microscope (SEM), it was confirmed that the crystal had a round shape of less than 100 nm.

[Table 3]

Example 3

The aluminosilicate reaction gel was prepared by first mixing 36.61 g of liquid sodium aluminate (LSA) (46.55% solution), 24.3 g of sodium hydroxide (50% solution) and 749.05 g of water under vigorous stirring. After complete mixing, 421.53 g of propyltrimethylammonium bromide (25% SACHEM) was added followed by 167.79 g of Ultrasil VN SP 89%. After this addition was complete, the resulting reaction mixture was homogenized for 1 hour and transferred to a 2 L Parr stainless steel stirred autoclave. The mixture crystallized at 175 DEG C with stirring at 350 RPM for 132 hours. The solid product was recovered by centrifugation, washed with deionized water and dried at 95 < 0 > C. This product was identified as being UZM-43 by XRD. Representative diffraction lines observed for the product are shown in Table 4 below. The product composition was determined by elemental analysis to have the following molar ratio: Si / Al = 13.05, Na / Al = 0.34. A portion of the material was calcined in air for 2 hours at 600 DEG C and then for 6 hours. The BET surface area was 292 m ² / g and the micropore volume was 0.101 cc / g. According to a scanning electron microscope (SEM), it was confirmed that the crystal had a round shape of less than 100 nm.

[Table 4]

Representative diffraction lines observed for the calcined UZM-43 are shown in Table 5 below.

[Table 5]

UZM-43 synthesized according to Example 1 and Example 2 was formulated as a catalyst containing 70% UZM-43 and 30% alumina. In the catalyst preparation, Catapal B alumina was first degassed with nitric acid using 0.17 g of HNO ₃ per g alumina Catapal B. The peptized alumina was then placed in a mill and mixed until a dough with a texture suitable for extrusion was formed. The dough was then extruded to form a 1/16 "diameter cylinder, which was dried overnight at 100 DEG C and then classified as having a length to diameter ratio of 3. This dry extrudate was placed in a box oven under flowing air The calcined support was exchanged with a 10 wt% NH ₄ NO ₃ solution for 1 hour at 75 ° C. This was followed by the addition of 10 g of water per g of zeolite The NH ₄ NO ₃ exchange and water washing were repeated two more times. The extrudate was then dried at 120 ° C for 4 hours and then activated at 550 ° C.

For each of the samples listed in Table 1, the observed diffraction pattern was compared to the DIFFaX simulation pattern to provide an estimate of the alpha N and alpha S transition probabilities indicating EUO, NES and NON clustering trends. Percentages of EUO, NES and NON were calculated from their transition probabilities. The best fit for the simulation is summarized in Table 6 below.

[Table 6]

Samples 1 and 2: The synthesized samples 1 and 2 have very similar diffraction patterns and can match the same DIFFaX simulated pattern. Both of which tend to cluster only in the EUO-like and NON-like regions that exhibit only a small tendency to cluster in the NES-like region and induce structures with more EUO and NON traits than the NES character .

Sample 3: The synthesized sample 3 has a slightly different diffraction pattern from the first two samples. The pattern may be suitable for a simulated pattern indicating that the sample contains slightly more NON traits and slightly less EUO traits than the first two samples.

The following observations were made regarding the diffraction of the samples of the prior art.

ERS-10. Among the literature samples, ERS-10 has the most similar diffraction pattern to the present invention, but there is a distinct difference. The pattern may be suitable for simulations showing similar compositions, but has a slightly higher EUO content than UZM-43 and a higher Si / Al ₂ ratio than UZM-43.

The diffraction pattern of SSZ-47 differs from that for Samples 1, 2 and 3 and is consistent with the structure containing more NON traits.

RUB-35 has the most diffractive pattern as for the samples illustrating the present invention. The pattern is consistent with a structure with high EUO traits. A model for faulting in RUB-35, which does not consider clustering, has been developed. The highest suitability of the pattern was achieved for structures with 78% EUO type features and 22% NON type features. The models reported here provide similar results (82% EUO, 12% NON, 8% NES) as well as some NES type traits.

Certain embodiments

It is to be understood that the following description is made in connection with the specific embodiments, which are intended to illustrate but not limit the scope of the foregoing description and the appended claims.

An embodiment of the present invention is a hydrocarbon conversion process comprising contacting a hydrocarbon stream with a catalyst at a hydrocarbon conversion condition to produce a converted product, wherein the catalyst comprises a modified UZM-43 microporous crystalline zeolite, UZM-43 has at least three-dimensional skeletons of AlO ₂ and SiO ₂ tetrahedral units, and an anhydrous-based experimental composition expressed by the following empirical formula,

에 의해 결정된 값을 갖고,Wherein m represents sodium or represents a combination of sodium and potassium exchangeable cations, "m" is the molar ratio of M to (Al + E) and varies from 0.05 to 5, and R1 is a single charged Quot; rl "is the molar ratio of R to (Al + E) and has a value of 0.25 to 8.0, R2 is an amine," r2 " X is the molar fraction of E and has a value of from 0 to 1.0, and "y" is the mole fraction of (Al +) and E is the element selected from the group consisting of gallium, iron, boron and mixtures thereof, E) is changed from more than 5 to 40, "z" is the molar ratio of O to (Al + E), and the equation:

Lt; / RTI >

The modified UZM-43 has an x-ray diffraction pattern having at least the d-spacing and the intensities shown in Table A below and is thermally stable to a temperature of at least 600 캜 and less than 420 m ² / g BET surface area.

[Table A]

Embodiments of the present invention are directed to a process wherein the hydrocarbon conversion process is carried out by a process comprising the steps of: alkylating, dealkylating, transalkylating, transalkylating, isomerizing an aromatic, alkylating an olefin with isoparaffin, olefin dimerization, olefin oligomerization, catalytic cracking, and dewaxing, , Or any of the preceding embodiments of the preceding paragraph, through the first embodiment of the preceding paragraph. An embodiment of the present invention is characterized in that the modified UZM-43 microporous crystalline zeolite has an EUO-NES-NON skeleton structure comprising 33-34 wt% EUO, 24-31 wt% NES and 34-43 wt% NON And any or all of the preceding yarn aspects of the preceding paragraph, in addition to the first embodiment of the preceding paragraph. Embodiments of the present invention are any, all, or any of the preceding embodiments of the foregoing paragraph, via the first embodiment of the foregoing paragraph, wherein the catalyst further comprises alumina.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Therefore, the above-described preferred specific embodiments should be construed as merely illustrative and not limitative of the remainder of the disclosure in any manner whatsoever.

In the foregoing, unless otherwise specified, all temperatures are set at Celsius temperature, and all parts and percentages are by weight.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined by the appended claims. And can be suitably applied to various uses and conditions.

Claims (7)

A process for hydrocarbon conversion comprising contacting a hydrocarbon stream with a catalyst under hydrocarbon conversion conditions to produce a converted product, wherein the catalyst comprises a modified UZM-43 microporous crystalline zeolite, wherein the modified UZM- Dimensional structure of AlO ₂ and SiO ₂ tetrahedral units, and an anhydrous-based experimental composition expressed by the following empirical formula,

Wherein m represents sodium or represents a combination of sodium and potassium exchangeable cations, "m" is the molar ratio of M to (Al + E) and varies from 0.05 to 5, and R1 is a single charged Quot; rl "is the molar ratio of R to (Al + E) and has a value of 0.25 to 8.0, R2 is an amine," r2 " X is the molar fraction of E and has a value of from 0 to 1.0, and "y" is the mole fraction of (Al +) and E is the element selected from the group consisting of gallium, iron, boron and mixtures thereof, E) is changed from more than 5 to 40, "z" is the molar ratio of O to (Al + E), and the equation:

Lt; RTI ID = 0.0 > a < / RTI &
The modified UZM-43 has an x-ray diffraction pattern having at least the d-spacing and the intensities shown in Table A below and is thermally stable to a temperature of at least 600 캜 and less than 420 m ² / g Lt; RTI ID = 0.0 > BET < / RTI > surface area.
[Table A]

The method of claim 1, wherein the hydrocarbon conversion process is carried out in the presence of an alkylation, dealkylation, transalkylation, isomerization of an aromatic, alkylation of an olefin with isoparaffin, olefin dimerization, olefin oligomerization, catalytic cracking and dewaxing ≪ / RTI > The process according to claim 1, wherein the hydrocarbon conversion process is a process consisting of xylene isomerization, toluene disproportionation, ring opening and cracking to remove the benzene co-boiler, and alkylation of the aromatic with paraffins ≪ / RTI > 3. The method of claim 2, wherein the hydrocarbon conversion process is an alkylation process. The method of claim 2, wherein the hydrocarbon conversion process is a catalytic cracking process. The method of claim 1, wherein the modified UZM-43 microporous crystalline zeolite has an EUO-NES-NON skeleton structure comprising 33-34 wt% EUO, 24-31 wt% NES, and 34-43 wt% NON How it is. The method of claim 1, wherein the catalyst further comprises alumina.

Images